Nature of the Electronic Ground State in Tris(2-chlorophenanthroline)iron(II) Perchlorate and Related Complexes
The orbital and spin ground states of [Fe(2-Cl(phen))3](ClO4)2 (phen = phenanthroline) and related high-spin ferrous complexes have been studied using Mössbauer spectroscopy. The temperature dependence of the Mössbauer spectrum of [Fe-(2-Cl(phen))3](ClO4)2 over the range 300-4.2°K indicates the system to have a ground spin quintet contrary to the results of a recent susceptibility study in which a high-spin to low-spin equilibrium is assumed. Magnetically perturbed Mössbauer spectra of the 2-Cl complex as well as the high-spin form of [Fe(phen)2(NCS)2] show these compounds to have a negative principal component (Vzz) of the electric field gradient tensor. This result is consistent with previous Mössbauer and magnetic studies of [Fe(phen)2X2] complexes (X- = Cl-, N3-) and is interpreted in terms of an electron in dz 2 corresponding to an orbital (2A) singlet ground term.
W. M. Reiff and G. J. Long, "Nature of the Electronic Ground State in Tris(2-chlorophenanthroline)iron(II) Perchlorate and Related Complexes," Inorganic Chemistry, vol. 13, no. 9, pp. 2150-2153, American Chemical Society (ACS), Sep 1974.
The definitive version is available at http://dx.doi.org/10.1021/ic50139a019
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